CN103524399A - Organic compound and electroluminescent device using same - Google Patents

Organic compound and electroluminescent device using same Download PDF

Info

Publication number
CN103524399A
CN103524399A CN201310495246.6A CN201310495246A CN103524399A CN 103524399 A CN103524399 A CN 103524399A CN 201310495246 A CN201310495246 A CN 201310495246A CN 103524399 A CN103524399 A CN 103524399A
Authority
CN
China
Prior art keywords
compound
preparation
add
ethanol
toluene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201310495246.6A
Other languages
Chinese (zh)
Other versions
CN103524399B (en
Inventor
贾学艺
吕瑶
许军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hebei Huaqing photoelectric material Co., Ltd.
Original Assignee
Green People's Science And Technology Ltd Co In Beijing
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Green People's Science And Technology Ltd Co In Beijing filed Critical Green People's Science And Technology Ltd Co In Beijing
Priority to CN201310495246.6A priority Critical patent/CN103524399B/en
Publication of CN103524399A publication Critical patent/CN103524399A/en
Application granted granted Critical
Publication of CN103524399B publication Critical patent/CN103524399B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/94—[b, c]- or [b, d]-condensed containing carbocyclic rings other than six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Abstract

The invention relates to an organic compound. The organic compound has a structure represented in a formula I, wherein R1, R2 and R3 are independently selected from hydrogen atom, substituted or non-substituted C1-C30 alkyl, substituted or non-substituted C1-C30 naphthenic base, substituted or non-substituted C1-C30 alkoxy, substituted or non-substituted C6-C30 aryl, substituted or non-substituted C6-C30 aryloxy, substituted or non-substituted C6-C30 arylamine, substituted or non-substituted C2-C30 heterocyclic ring, substituted or non-substituted C6-C30 condensed polycyclic group, hydroxyl, cyano group and substituted or non-substituted amino, respectively. Furthermore, the invention relates to an electroluminescent device, wherein the electroluminescent device comprises a hole injection layer and/or a hole transport layer using at least one of the compounds.

Description

A kind of organic compound and use the electroluminescent device of this organic compound
Technical field
The present invention relates to a kind of organic compound, be specifically related to a kind of naphtho-nitrogen heterocycles derivative for organic electroluminescence device and in the application in electroluminescent technique of display field.
Background technology
Organic electroluminescent technology, Organic Light Emitting Diode technology, is regarded as technique of display of future generation.Compare with traditional liquid crystal (Liquid Crystal Display, LCD) technology, without backlight, irradiate and colour filter, but pixel self is luminous, be presented on colored display panel.And, have superelevation contrast gradient, super wide visible angle, curved surface, the characteristic such as slim.
Organic electroluminescence device can be traced back to the earliest the people such as Pope in 1963 research and take blue coloured electroluminous that anthracene is single-chip (10-20 μ m), because the restriction of the thicker electrode materials with using of anthracene single crystal luminescent layer, the luminous trigger voltage of device is up to 400V, and efficiency and brightness lower.Yet this does not affect the status that it is gone through in organic electroluminescent LED (OLED) development, between two more than ten years after this, the progress of organic electroluminescent is always very slow.Until the C.W.Tang of 1987 Nian， Kodaks etc. develop bilayer structure with oxine aluminium (Alq 3) do that luminescent layer, aromatic diamines are made hole transmission layer, ITO makes anode, Mg ︰ Ag(10:1) alloy makes " sandwich " type device of negative electrode, just opens the chapter that OLED device is new.The nineteen ninety Cavendish of Cambridge University finds again in laboratory to take the EL luminescent device that polymkeric substance is main body, another new way of having opened up El element.In the then more than ten years, due to high-res RGB colour element, the restriction of TFT backboard and the difficulty in big area, the progress of OLED is always very slow.And people become the focus of flat pannel display to the research of OLED in recent years, along with device technology reaches its maturity, design of material, synthetic continuous improvement, hexyl has originally been realized the dream of the volume production of full color " OLED illusion indicating meter ".
In organic electroluminescence device research, material plays conclusive effect, because film in its preparation technology is with vacuum vapour deposition preparation, is unformed shape.The crystallization of material is considered to the major cause of device aging by luminescent properties is declined.In view of this, in thin film preparation process, conventionally need to adopt adequate measures to reduce or stop the crystallization of organic layer material.The first, increase the asymmetry of molecular structure; The second, increase the sterically hindered of molecular structure, reduce molecular aggregates.
Although known OLED material has before very large lifting performance at present, does not also reach gratifying luminous efficiency, life-span and optical purity.
Therefore, the OLED material of exploitation stability and high efficiency, improves device efficiency, extends device lifetime, improves optical purity, has very important practical significance.
Summary of the invention
The present invention passes through molecular designing, synthesize series of new electroluminescent material, can be used on hole transmission layer, hole injection layer and optically coupled layers, greatly reduce the trigger voltage of device, improved the current efficiency of device, make device there is higher luminous efficiency, in the longer life-span, improved the purity of light simultaneously.
In order to realize above-mentioned device performance, the technical solution used in the present invention is as follows:
The invention provides a kind of organic compound, it has suc as formula the structure shown in I:
Figure BDA0000399101360000021
Wherein:
R 1, R 2and R 3be selected from independently of one another hydrogen atom, replacement or unsubstituted C1-C30 alkyl, replacement or unsubstituted C1-C30 cycloalkyl, replacement or unsubstituted C1-C30 alkoxyl group, replacement or unsubstituted C6-C30 aryl, replacement or do not replace C6-C30 aryloxy, replacement or do not replace C6-C30 aryl amine, replacement or unsubstituted C2-C30 heterocycle, replacement or do not replace C6-C30 thick and many cyclic groups, hydroxyl, cyano group and replace unsubstituted amino.
In a preferred implementation of compound of the present invention, described C6-C30 aryl is selected from phenyl, xenyl, naphthyl or anthryl.
In a preferred implementation of compound of the present invention, described compound is selected from the compound with the structure shown in G1-G20:
Figure BDA0000399101360000031
Figure BDA0000399101360000041
The present invention also provides a kind of electroluminescent device, comprise use in above-claimed cpd at least one as hole injection layer and/or hole transmission layer.
In a preferred implementation of electroluminescent device of the present invention, described device comprises substrate and is cascadingly set on anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the negative electrode on substrate.
In a preferred implementation of electroluminescent device of the present invention, described device also comprises optically coupled layers, on its setting and described negative electrode.
In a preferred implementation of electroluminescent device of the present invention, the material of described optically coupled layers is selected from least one in compound of the present invention.
In a preferred implementation of electroluminescent device of the present invention, described anode material is selected from least one in tin indium oxide, indium zinc oxide and tindioxide.
In a preferred implementation of electroluminescent device of the present invention, described luminescent layer material is selected from two carbazole biphenyl, 9,10-bis-(2-naphthyl) anthracene, Ir (ppy 3) or two carbazole biphenyl and the Ir (ppy of TPBi doping 3) or TPBi doping 9, at least one in 10-bis-(2-naphthyl) anthracene.
In a preferred implementation of electroluminescent device of the present invention, described electric transmission layer material is selected from 4,7-phenylbenzene-1, at least one in 10-phenanthroline and three (oxine) aluminium.
In a preferred implementation of electroluminescent device of the present invention, described negative electrode is selected from least one in magnesium, aluminium and silver.
Beneficial effect of the present invention:
Compound provided by the invention is a kind of unsymmetrical structure, add other base group modification, make material there is higher carrier injection and transmittability, compound of the present invention also has excellent heat-staple performance, higher second-order transition temperature, larger triplet, and then obtain organic electroluminescence device of the high and low driving voltage of a kind of luminous efficiency, long lifetime, high brightness, high color purity, can be used as novel light-emitting center and use.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the electroluminescent device according to the present invention;
Fig. 2 is the absorption spectrum of compound G11 in the present invention;
Fig. 3 is the emmission spectrum of compound G11 in the present invention;
Fig. 4 is the hot weightless picture of compound G11 in the present invention.
Embodiment
Below in conjunction with drawings and Examples, the preferred embodiments of the invention are elaborated, but scope of the present invention is not limited to following examples.
Compou nd synthesis embodiment
Embodiment 1: the preparation of compound G1
The first step: the intermediate A of preparation preparation as follows:
Figure BDA0000399101360000061
(1) intermediate A-1 is synthetic:
In the first reactor, add respectively o-bromobenzoic acid methyl esters 21.5g(0.1mole), 1-naphthalene boronic acids 17.2g(0.1mole), salt of wormwood 41.5g(0.3mole), toluene 200ml, ethanol 100ml, water 100ml, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 2.3g(0.002mole), being warming up to refluxes spends the night, point board monitoring is to reacting completely, finish reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing separates organic phase, be spin-dried for and used ethanol heat to boil twice to obtain 21g solid intermediate A-1, yield 80%.
(2) intermediate A-2, A-3's is synthetic:
In the second reactor, add 2.62g(0.01mole) intermediate A-1, tetrahydrofuran (THF) (THF) 50ml, pass into nitrogen protection, cryosel is bathed and is cooled to sub-zero zero, slowly drips 35ml lithium methide (CH 3li), heat release is violent, and solution reddens, within 15 minutes, dropwise, insulated and stirred 30 minutes, removes ice-water bath, naturally heats up, stirring at room 1 hour, water quencher, hydrochloric acid is adjusted to acidity, and layering obtains organic phase, water is extracted with ethyl acetate, and merges organic phase and is spin-dried for to obtain oily matter intermediate A-2.In this oily matter, add 100ml acetic acid, several hydrochloric acid, are heated to reflux, and add 150ml water after cooling, separate out solid, filter washing, cross silicagel column and obtain 1.6g solid intermediate A-3.Total recovery 65%.
(3) intermediate A-4 is synthetic:
In the 3rd reactor, add 2.44g(0.01mole) intermediate A-3,60ml dimethyl formamide (DMF), make it to dissolve completely, under stirring at room, drip 1.78g(0.01mole) the DMF solution (30 quality %) of N-bromosuccinimide (NBS), 30 minutes used times, drip Bi Jixu stirring reaction after 1 hour, stopped reaction.Add elutriation and go out solid and filter, ethanol drip washing, toluene for crude product-ethanol system recrystallization, obtains 2.6g solid intermediate A-4, yield 80%.
(4) intermediate A-5 is synthetic:
In the 4th reactor, add respectively 3.23g(0.01mole) intermediate A-4, ortho-nitrophenyl boric acid 2.5g(0.015mole), salt of wormwood 4.15g(0.03mole), toluene 30ml, ethanol 15ml, water 15ml, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), be warming up to backflow, point board monitoring is to reacting completely, stopped reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain 3g solid intermediate A-5, yield 80%.
(5) intermediate A-6 is synthetic:
In the 5th reactor, add 3.65g(0.01mole) intermediate A-5, then add 60ml DMF, make it to dissolve completely, under stirring at room, add in three batches 1.78g(0.01mole) NBS, 30 minutes used times, drip Bi Jixu reaction 1 hour, stopped reaction, adds elutriation and goes out solid and filter, ethanol drip washing, toluene for crude product-ethanol system recrystallization, obtains 3.5g solid intermediate A-6, yield 80%.
(6) intermediate A-7 is synthetic:
In the 6th reactor, add respectively 4.44g(0.01mole) intermediate A-6,37ml triethoxy phosphorus [P (OEt) 3], 37ml1,2-dichlorobenzene, stirs 9 hours at 150 ℃, then coolingly with distilled water wash, boils off solvent and obtains oily matter afterwards, adds methylene dichloride to dissolve, post separated 3g off-white color solid intermediate A-7, yield 75%.
(7) intermediate A is synthetic:
In the 7th reactor, add respectively 4.12g(0.01mle) intermediate A, iodobenzene 2.04g(0.01mole), salt of wormwood 4.14g(0.03mole), copper powder 0.064g(0.001mloe), phenanthroline 0.198g(0.001mole), dimethylbenzene 50ml, be heated to reflux, reaction is spent the night, point board monitoring is to after reacting completely, lower the temperature, add toluene 100ml to filter, filtrate is spin-dried for, and with ethanol-toluene system recrystallization, obtains 3.9g solid intermediate A, yield 80%.
Prepare core compound B, its structural formula and synthetic route are as follows:
Second step: prepare target compound G1
The compound G1 of the required preparation of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000081
Concrete reaction process comprises:
(1) preparation of intermediate G1-2:
By 2.86g(0.01mole) 1, 4-dibromine naphthalene, phenylo boric acid 1.21g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, finish reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100 water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain 2.3g solid intermediate G1-2, yield 80%.
(2) preparation of intermediate G1-2:
By 2.83g(0.01mole) intermediate G1-1,2-be amino-9,9-dimethyl fluorene 2.09g(0.01mole) and 50ml toluene mixing, under nitrogen atmosphere, adding 0.18g(0.0002mole) three (dibenzalacetones) close two palladium Pd 2(dba) 3, 1.44g(0.015mole) potassium tert.-butoxide and 0.809g(0.0004mole, 10 quality % toluene solutions) tri-butyl phosphine, be heated to 80 ℃ and react, some board monitoring, is cooled to room temperature after reacting completely, add 100ml toluene, cross silica gel funnel and obtain filtrate, filtrate water washing obtains organic phase 3 times, is spin-dried for the rear silicagel column of crossing, obtain 3.3g solid intermediate G1-2, yield 80%.
(3) preparation of intermediate G1-3:
By 4.88g(0.01mole) intermediate A, 4.11g(0.01mole) intermediate G1-2 and 50ml toluene mixes, and under nitrogen atmosphere, adds 0.18g(0.0002mole) Pd2 (dba) 3, 1.44g(0.015mole) potassium tert.-butoxide and 0.809g(0.0004mole, 10 quality % toluene solutions) tri-butyl phosphine, is heated to 85 ℃ and reacts, some board monitoring, after reacting completely, be cooled to room temperature, add 100ml toluene, cross silica gel funnel, collect filtrate, filtrate water washing obtains organic phase 3 times, be spin-dried for the rear silicagel column of crossing, obtained 6.4g solid intermediate G1-3, yield 78%.
(4) preparation of intermediate G1-4:
By 8.19g(0.01mole) intermediate G1-3 is placed in 60ml DMF, make it to dissolve completely, under stirring at room, drip 1.78g(0.0095mole) the DMF solution (30 quality %) of NBS, 30 minutes used times, continues reaction after 1 hour, stopped reaction, add elutriation and go out solid and filter, ethanol drip washing, with toluene-ethanol system recrystallization, obtain 7.18g solid intermediate G1-4, yield 80%.
(5) preparation of compound G1:
By 8.98g(0.01mole) compound G-4, triphenylene-2-boric acid 2.72g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml, water 30ml, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, finish reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate is used 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain 8.3g faint yellow solid compound G1, yield 80%.MS(m/e): 1044.44, ultimate analysis: C 80h 56n 2, theoretical value C:91.92, H:5.40, N:2.68; Measured value C:91.87, H:5.42, N:2.71.
Embodiment 2: the preparation of compound G2
The preparation of the target compound G2 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000101
Concrete, the preparation method of compound of the present invention comprises:
(1) intermediate G1-4 is according to the same method preparation of embodiment 1;
(2) by 8.98g(0.01mole) intermediate G1-4, fluoranthene-3-boric acid 2.46g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole) react, be warming up to backflow, point board monitoring is to reacting completely, finish reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain 7.6g faint yellow solid compound G2, yield 75%.MS(m/e): 1018.43, ultimate analysis: C 78h 54n 2, theoretical value C:91.91, H:5.34, N:2.75; Measured value C:91.90, H:5.35, N:2.75.
Embodiment 3: the preparation of compound G3
The preparation of the target compound G3 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000102
Concrete, the preparation method of described compound G3 comprises:
(1) intermediate G1-4 is according to the same method preparation of embodiment 1;
(2) by 8.48g(0.01mole) intermediate G1-4, 3, 5-diphenyl benzene boric acid 2.74g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole) react, be warming up to backflow, point board monitoring is to reacting completely, finish reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing separates organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain 7.7g solid chemical compound G3, yield 77%.MS（m/e）：996.44，。Ultimate analysis: C 76h 56n 2, theoretical value C:91.53, H:5.66, N:2.81; Measured value C:91.55, H:5.63, N:2.82.
Embodiment 4: the preparation of compound G4
The preparation of the target compound G4 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000111
Concrete, the preparation method of described compound G4 comprises:
(1) intermediate G1-4 is according to the same method preparation of embodiment 1;
(2) by 8.48g(0.01mole) intermediate G1-4, 9, 9-spiral shell two fluorenes-2-boric acid 3.6g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole) react, be warming up to backflow, point board monitoring is to reacting completely, finish reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing separates organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain 7.58g faint yellow solid compound G4, yield 70%.MS(m/e): 1082.46, ultimate analysis: C 83h 58n 2, theoretical value C:92.02, H:5.40, N:2.59; Measured value C:92.00, H:5.41, N:2.59.
Embodiment 5: the preparation of compound G5
The preparation of the target compound G5 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000112
Figure BDA0000399101360000121
Concrete, the preparation method of described compound G5 comprises:
(1) preparation of intermediate G5-1:
In the first container, add 3.33g(0.03mole) adjacent fluoroaniline, then add 60ml DMF, make it to dissolve completely, under stirring at room, drip 28.92g(0.06mole) the DMF solution of tetrabutyl tribromide ammonium, 30 minutes used times, drips and finishes, continue reaction after 1 hour, react substantially complete.Add elutriation and go out solid and filter, and use ethanol drip washing, with toluene-ethanol system recrystallization, obtain solid intermediate G5-1, yield 80%.
(2) preparation of intermediate G5-2:
In second container, add respectively 2.69g(0.01mole) intermediate G5-1, phenylo boric acid 2.44g(0.02mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, close heating, be spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain the white solid intermediate G5-2 of class, yield 70%.
(3) preparation of intermediate G5-3:
In the 3rd container, add respectively 2.63g(0.01mole) intermediate G5-2, bromobenzene 1.22g(0.01mole) and 50ml toluene, under nitrogen atmosphere, add 0.18g(0.0002mole) Pd 2(dba) 3, 1.44g(0.015mole) potassium tert.-butoxide and 0.809g(0.0004mole, 10 quality % toluene solutions) tri-butyl phosphine, be heated to 70 ℃ and react, some board monitoring, is cooled to room temperature after reacting completely, add 100ml toluene, cross silica gel funnel and obtain filtrate, filtrate water is washed 3 times to obtain organic phase, is spin-dried for the rear silicagel column of crossing, obtain solid intermediate G5-3, yield 75%.
(4) preparation of intermediate G5-4:
Intermediate A is provided, and intermediate A is according to the same method preparation of embodiment 1;
By 3.39g(0.01mole) intermediate G5-3,4.88g(0.01mole) intermediate A and the mixing of 50ml toluene, under nitrogen atmosphere, add 0.18g(0.0002mole) Pd 2(dba) 3, 1.44g(0.015mole) potassium tert.-butoxide and 0.809g(0.0004mole, 10 quality % toluene solutions) tri-butyl phosphine, be heated to 70 ℃ and react, some board monitoring, is cooled to room temperature after reacting completely, add 100ml toluene, cross silica gel funnel and obtain filtrate, filtrate water is washed 3 times to obtain organic phase, is spin-dried for the rear silicagel column of crossing, obtain solid intermediate G5-4, yield 75%.
(5) preparation of intermediate G5-5:
In the 4th container, add 14.94g(0.02mole) intermediate G5-4, then add 100ml DMF, make it to dissolve completely, under stirring at room, drip 1.78g(0.0095mole) the DMF solution (30 quality %) of NBS, 30 minutes used times, continue reaction after 1 hour, stopped reaction, adds elutriation and goes out solid and filter, ethanol drip washing, with toluene-ethanol system recrystallization, obtain solid intermediate G5-5, yield 70%.
(6) preparation of compound G5:
By 8.25g(0.01mole) intermediate G5-5, fluoranthene-3-boric acid 2.46g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml, pass into nitrogen 10 minutes, then add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, close heating, be spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing separates organic phase, be spin-dried for and used ethanol heat to boil twice, obtain faint yellow solid compound G5, yield 70%.MS(m/e): 946.37, ultimate analysis: C 71h 47fN 2, theoretical value C:90.03, H:5.00, F:2.01, N:2.96; Measured value C:90.04, H:4.96, F:2.02, N:2.98.
Embodiment 6: the preparation of compound G6
The preparation of the target compound G6 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000131
Figure BDA0000399101360000141
Concrete, the preparation method of described compound G6 comprises:
(1) preparation of intermediate G6-1:
Intermediate A is provided, and intermediate A is according to the same method preparation of embodiment 1;
By 3.21g(0.01mole) two-(4-xenyl) amine, 4.88g(0.01mole) intermediate A and 50ml toluene, under nitrogen atmosphere, add 0.18g(0.0002mole) Pd 2(dba) 3, 1.44g(0.015mole) potassium tert.-butoxide and 0.809g(0.0004mole, 10 quality % toluene solutions) tri-butyl phosphine, be heated to 70 ℃ and react, some board monitoring, is cooled to room temperature after reacting completely, add 100ml toluene, cross silica gel funnel and obtain filtrate, filtrate water is washed 3 times to obtain organic phase, is spin-dried for the rear silicagel column of crossing, obtain solid intermediate G6-1, yield 75%.
(2) preparation of intermediate G6-2:
By 7.29g(0.01mole) intermediate G6-1 adds in 100ml DMF, make it to dissolve completely, under stirring at room, drip 1.78g(0.0095mole) the DMF solution (30 quality %) of NBS, 30 minutes used times, continues reaction after 1 hour, stopped reaction, add elutriation and go out solid and filter, ethanol drip washing, with toluene-ethanol system recrystallization, obtain solid intermediate G6-2, yield 70%.
(3) preparation of compound G6:
By 8.08g(0.01mole) intermediate G6-2, fluoranthene-3-boric acid 2.46g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, pass into nitrogen 10 minutes, then add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, close heating, be spin-dried for, add 100ml methylene dichloride, 100ml water, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing separates organic phase, be spin-dried for and used ethanol heat to boil twice, obtain faint yellow solid compound G6, yield 70%.MS(m/e): 928.38, ultimate analysis: C 71h 48n 2, C:91.78, H:5.21, N:3.01; Measured value C:91.80, H:5.22, N:2.98.
Embodiment 7: the preparation of compound G7
The preparation of the target compound G7 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000151
Concrete, the preparation method of described compound G7 comprises:
(1) preparation of intermediate G7-1:
Intermediate A is provided, and intermediate A is according to the same method preparation of embodiment 1;
By 2.19g(0.01mole) N-phenyl-N-(1-naphthyl) amine, 4.88g(0.01mole) intermediate A and 50ml toluene mixes, and passes into nitrogen after 10 minutes, then adds 0.18g(0.0002mole) Pd 2(dba) 3, 1.44g(0.015mole) potassium tert.-butoxide and 0.809g(0.0004mole, 10 quality % toluene solutions) tri-butyl phosphine, be heated to 70 ℃ and react, some board monitoring, is cooled to room temperature after reacting completely, add 100ml toluene, cross silica gel funnel and obtain filtrate, filtrate water is washed 3 times to obtain organic phase, is spin-dried for the rear silicagel column of crossing, obtain solid intermediate G7-1, yield 80%.
(2) preparation of intermediate G7-2:
By 6.27g(0.01mole) intermediate G7-1 adds in 100ml DMF, make it to dissolve completely, under stirring at room, drip 1.78g(0.0095mole) the DMF solution (30 quality %) of NBS, 30 minutes used times, continues reaction after 1 hour, stopped reaction, add elutriation and go out solid and filter, ethanol drip washing, with toluene-ethanol system recrystallization, obtain solid intermediate G7-2, yield 70%.
(3) preparation of compound G7:
By 7.05g(0.01mole) intermediate G7-2, 3, 5-diphenyl benzene boric acid 2.74g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, pass into nitrogen 10 minutes, then add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), be warming up to backflow, point board monitoring is to reacting completely, close heating, be spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing separates organic phase, be spin-dried for, and boil twice by ethanol heat, obtain faint yellow solid compound G7, yield 77%.MS(m/e): 854.37, ultimate analysis: C 65h 46n 2, theoretical value C:91.30, H:5.42, N:3.28; Measured value C:91.28, H:5.44, N:3.28
Embodiment 8: the preparation of compound G8
The preparation of the target compound G8 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000161
Concrete, the preparation method of described compound G8 comprises:
(1) preparation of intermediate G8-1:
Intermediate A is provided, and intermediate A is according to the same method preparation of embodiment 1;
10g intermediate A (0.02mole) is added in 150ml THF, be cooled to-78 ℃, at-78 ℃, drip 12ml(2.5M/L, 0.03mole) n-BuLi, be incubated 30 minutes, drip 4.26g (0.041mole) trimethyl borate, react after 2 hours and finish to react, in reaction solution, add water 50ml, stir 20 minutes, salt adding acid for adjusting pH value is to acid, stir 30 minutes, reaction solution is extracted with ethyl acetate three times, merge organic layer washing once, separate organic phase, organic liquor is spin-dried for, sherwood oil heat is boiled twice, filter, obtain the white solid intermediate G8-1 of class, yield 60%.
(2) preparation of intermediate G8-2:
By 4.53g(0.01mole) intermediate G8-1, 2.68g(0.01mole) 2-chloro-4, 6-phenylbenzene triazine, salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, then add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, stopped reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it to dissolve completely and cross silicagel column, filtrate adds water 100ml, washing separates organic phase, be spin-dried for, solid boils twice by ethanol heat, obtain off-white color solid intermediate G8-2, yield 75.4%.
(3) preparation of intermediate G8-3:
By 6.41g(0.01mole) intermediate G8-3 adds 100ml DMF, fully stir, make it to dissolve completely, under room temperature, drip 1.78g(0.01mole) the DMF solution (30 quality %) of NBS, 30 minutes used times, drip Bi Jixu stirring reaction 1 hour, add elutriation and go out solid, filter, and use ethanol drip washing, with toluene-ethanol system recrystallization, obtain solid intermediate G8-3, yield 70%.
(4) preparation of compound G8:
By 7.20g(0.01mole) intermediate G8-3, 3, 5-diphenyl benzene boric acid 2.74g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, close heating, be spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds water 100ml, washing, separate organic phase, be spin-dried for, and boil twice by ethanol heat, obtain white solid compound G8, yield 77%.MS(m/e): 868.36, ultimate analysis: C 64h 44n 4, theoretical value C:88.45, H:5.10, N:6.45; Measured value C:88.40, H:5.12, N:6.48.
Embodiment 9: the preparation of compound G9
The preparation of the target compound G9 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000171
Concrete, the preparation method of described compound G9 comprises:
(1) preparation of intermediate G9-1:
7g2-(4-bromophenyl)-1-phenyl benzoglyoxaline (0.02mole) is added in 150ml THF, be cooled to-78 ℃, at-78 ℃, drip 12ml(2.5M/L, 0.03mole) n-BuLi, be incubated 30 minutes, drip 4.26g (0.041mole) trimethyl borate, react after 2 hours and finish to react, in reaction solution, add water 50ml, stir 20 minutes, salt adding acid for adjusting pH value is to acid, stir 30 minutes, reaction solution is extracted with ethyl acetate three times, merge organic layer washing once, separate organic phase, be spin-dried for, solid boils twice by sherwood oil heat, filter, obtain the white solid intermediate G9-1 of class, yield 65%.
(2) preparation of intermediate G9-2:
Intermediate A is provided, and intermediate A is according to the same method preparation of embodiment 1;
By 3.14g(0.01mole) intermediate G9-1, 4.88g(0.01mole) intermediate A, salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), temperature rising reflux reacts for 5 hours, point board monitoring is to reacting completely, close heating, reaction solution is spin-dried for, add 100ml methylene dichloride, make it to dissolve completely and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, organic phase is spin-dried for and uses ethanol heat to boil twice, filter, obtain white solid intermediate G9-2, yield 75%.
(3) preparation of intermediate G9-3:
By 6.78g(0.01mole) intermediate G9-2 adds 100ml DMF, makes it to dissolve completely, drips 1.78g(0.01mole under stirring at room) the DMF solution (30 quality %) of NBS, 30 minutes used times, drip Bi Jixu room temperature reaction 1 hour.Add elutriation and go out solid and filter, use ethanol drip washing, with toluene-ethanol system recrystallization, obtain solid intermediate G9-3, yield 70%.
(4) preparation of compound G9:
By 7.56g(0.01mole) intermediate G9-3, fluoranthene-3-boric acid 2.46g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, stop reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain white solid compound G9, yield 77%.MS(m/e): 877.35, ultimate analysis: C 66h 43n 3, theoretical value C:90.28, H:4.94, N:4.79; Measured value C:90.35, H:4.91, N:4.84.
Embodiment 10: the preparation of compound G10
The preparation of the target compound G10 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000181
Figure BDA0000399101360000191
Concrete, the preparation method of described compound G8 comprises:
(1) preparation of intermediate G10-1:
Intermediate A is provided, and intermediate A is according to the same method preparation of embodiment 1;
By 2.12g(0.01mole) diphenylene-oxide-4-boric acid, 4.88g(0.01mole) intermediate A, salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, react 5 hours, react complete, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain white solid intermediate G10-1, yield 73%.
(2) preparation of intermediate G10-2:
By 5.76g(0.01mole) intermediate G10-1 adds in 100ml DMF, makes it to dissolve completely, drips 1.78g(0.01mole under stirring at room) the DMF solution (30 quality %) of NBS, 30 minutes used times, continue reaction 1 hour, stopped reaction.Add elutriation and go out solid and filter, ethanol drip washing, toluene for crude product-ethanol system recrystallization, obtains solid intermediate G10-2, yield 70%.
(3) preparation of compound G10:
By 6.56g(0.01mole) intermediate G10-2, 1-pyrene boric acid 2.48g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, finish reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain white solid compound G10, yield 73%.MS(m/e): 777.30, ultimate analysis: C 59h 39nO, theoretical value C:91.09, H:5.05, N:1.80, O:2.06; Measured value C:91.09, H:5.10, N:1.78, O:2.03.
Embodiment 11: the preparation of compound G11
The preparation of the target compound G11 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000201
Concrete, the preparation method of described compound G8 comprises:
(1) preparation of intermediate G11-1:
Intermediate A is provided, and intermediate A is according to the same method preparation of embodiment 1;
By 2.12g(0.01mole) diphenylene-oxide-2-boric acid, 4.88g(0.01mole) intermediate A, salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, finish reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain white solid intermediate G11-1, yield 73%.
(2) preparation of intermediate G11-2:
By 5.76g(0.01mole) intermediate G11-1 adds in 100ml DMF, makes it to dissolve completely, drips 1.78g(0.01mole under stirring at room) the DMF solution (30 quality %) of NBS, 30 minutes used times, continue reaction and within 1 hour, finish reaction.Add elutriation and go out solid and filter, ethanol drip washing, toluene for crude product-ethanol system recrystallization, obtains solid intermediate G11-2, yield 70%.
(3) preparation of compound G11:
By 6.56g(0.01mole) intermediate G11-2, fluoranthene-3-boric acid 2.46g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, finish reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain white solid compound G11, yield 73%.MS(m/e): 775.29, ultimate analysis: C 59h 37nO, theoretical value C:91.33, H:4.81, N:1.81, O:2.06; Measured value C:91.35, H:4.82, N:1.77, O:2.06.
The Absorption and emission spectra of compound G11 in the present embodiment as shown in Figures 2 and 3, has the absorption spectrum of Fig. 2 to find out, G11 mainly absorbs the UV-light of 200-350nm section, and from emmission spectrum, the utilizing emitted light of G11 is mainly the blue light of 450-550nm section.By hot weightless picture, can be found out, G11 demonstrates satisfactory stability at 450 ℃.
Embodiment 12: the preparation of compound G12
The compound G12 of the required preparation of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000211
Concrete, the preparation method of described compound G8 comprises:
(1) preparation of intermediate G12-1:
Intermediate A is provided, and intermediate A is according to the same method preparation of embodiment 1;
By 2.28g(0.01mole) dibenzothiophene-4-boric acid, 4.88g(0.01mole) intermediate A, salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), temperature rising reflux reacts for 5 hours, point board monitoring is to reacting completely, stopped reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain white solid intermediate G12-1, yield 70%.
(2) preparation of intermediate G12-2:
By 5.92g(0.01mole) intermediate G12-1 adds in 100ml DMF, make it to dissolve completely, stirring at room dropping 1.78g(0.01mole) the DMF solution (30 quality %) of NBS, 30 minutes used times, drips Bi Jixu reaction 1 hour, react complete, adding elutriation goes out solid and filters ethanol drip washing, toluene for crude product-ethanol system recrystallization, obtain solid intermediate G12-2, yield 72%.
(3) preparation of compound G12:
By 6.7g(0.01mole) intermediate G12-2, fluoranthene-3-boric acid 2.46g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, finish reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain off-white color solid chemical compound G12, yield 70%.MS(m/e): 791.26, ultimate analysis: C 59h 37nS, theoretical value C:89.47, H:4.71, N:1.77, S:4.05; Measured value C:89.50, H:4.72, N:1.75, S:4.03.
Embodiment 13: the preparation of compound G13
The preparation of the target compound G13 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000221
Concrete, the preparation method of described compound G8 comprises:
(1) preparation of intermediate G13-1:
Intermediate A is provided, and intermediate A is according to the same method preparation of embodiment 1;
By 2.28g(0.01mole) dibenzothiophene-2-boric acid, 4.88g(0.01mole) intermediate A, salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), temperature rising reflux reacts for 5 hours, point board monitoring is to reacting completely, finish reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain white solid intermediate G13-1, yield 70%.
(2) preparation of intermediate G13-2:
By 5.92g(0.01mole) intermediate G13-1 adds in 100ml DMF, make it to dissolve completely, stirring at room dropping 1.78g(0.01mole) the DMF solution (30 quality %) of NBS, 30 minutes used times, drips Bi Jixu stirring reaction 1 hour, stopped reaction, adding elutriation goes out solid and filters ethanol drip washing, toluene for crude product-ethanol system recrystallization, obtain solid intermediate G13-2, yield 72%.
(3) preparation of compound G13:
By 6.7g(0.01mole) compound G13-2, 9, 9-diphenylfluorene-2-boric acid 3.6g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, finish reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain white solid compound G13, yield 70%.MS(m/e): 907.33, ultimate analysis: C 68h 45nS, theoretical value C:89.93, H:4.99, N:1.54, S:3.53; Measured value C:89.90, H:4.98, N:1.55, S:3.57.
Embodiment 14: the preparation of compound G14
Be prepared as follows intermediate B;
Intermediate A-7 are provided, and intermediate A-7 are according to the same method preparation of embodiment 1;
By 4.12g(0.01mle) intermediate A-7,4-iodine biphenyl 2.8g(0.01mole), salt of wormwood 4.14g(0.03mole), copper powder 0.064g(0.001mloe), phenanthroline 0.198g(0.001mole) and dimethylbenzene 50ml mix, be heated to reflux and react, point board monitoring is to after reacting completely, lower the temperature, add toluene 100ml to filter, filtrate is spin-dried for, with ethanol-toluene system recrystallization, obtain solid intermediate B, yield 80%.
Figure BDA0000399101360000231
The preparation of the target compound G14 of the present embodiment, its structural formula and synthetic route are as follows:
Concrete, the preparation method of described compound G8 comprises:
(1) preparation of intermediate G14-1:
Intermediate B is provided, and described intermediate B is according to the method preparation of the present embodiment;
Intermediate G1-2 is provided, and described intermediate G1-2 is according to the method preparation of embodiment 1;
By 5.64g(0.01mole) intermediate B, 4.12g(0.01mole) intermediate G1-2 and 50ml toluene mixes, and under nitrogen atmosphere, adds 0.18g(0.0002mole) Pd 2(dba) 3, 1.44g(0.015mole) potassium tert.-butoxide and 0.809g(0.0004mole, 10 quality % toluene solutions) tri-butyl phosphine, be heated to 70 ℃ and react, some board monitoring, is cooled to room temperature after reacting completely, add 100ml toluene, cross silica gel funnel and obtain filtrate, filtrate water extraction obtains organic phase 3 times, is spin-dried for the rear silicagel column of crossing, obtain solid intermediate G14-1, yield 75%.
(2) preparation of intermediate G14-2:
By 8.9g(0.01mole) intermediate G14-1 adds in 100ml DMF, makes it to dissolve completely, drips 1.78g(0.01mole under stirring at room) the DMF solution (30 quality %) of NBS, 30 minutes used times, drip Bi Jixu reaction after 1 hour, stopped reaction.Add elutriation and go out solid and filter, ethanol drip washing, toluene for crude product-ethanol system recrystallization, obtains solid intermediate G14-2, yield 70%.
(3) preparation of compound G14:
By 9.74g(0.01mole) intermediate G14-2, 3, 5-diphenyl benzene boric acid 2.74g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, finish reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain white solid compound G14, yield 77%.MS(m/e): 1122.49, ultimate analysis: C 88h 62n 2, theoretical value C:91.94, H:5.56, N:2.49; Measured value C:91.90, H:5.60, N:2.50.
Embodiment 15: the preparation of compound G15
The preparation of the target compound G15 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000251
Concrete, the preparation of compound G15 comprises the following steps:
(1) preparation of intermediate G15-1
Intermediate B is provided, and described intermediate B is according to the method preparation in embodiment 14;
Intermediate G1-2 is provided, and described intermediate G1-2 is according to the method preparation in embodiment 1;
By 5.64g(0.01mol) intermediate B, 3.61g(0.01mol) intermediate G1-2 and 50ml toluene mixes, and under nitrogen atmosphere, adds 0.18g(0.0002mol) Pd 2(dba) 3, 1.44g(0.015mol) potassium tert.-butoxide, 0.809g(0.0004mole, 10 quality % toluene solutions) tri-butyl phosphine, be heated to 70 ℃ and react, some board monitoring, is cooled to room temperature after reacting completely, add 100ml toluene, cross silica gel funnel and obtain filtrate, filtrate water extraction obtains organic phase 3 times, is spin-dried for the rear silicagel column of crossing, obtain solid intermediate G15-1, yield 75%.
(2) preparation of intermediate G15-2:
By 8.45g(0.01mol) intermediate G15-1 adds in 100ml DMF, makes it to dissolve completely, drips 1.78g(0.01mol under stirring at room) the DMF solution (30 quality %) of NBS, 30 minutes used times, drip Bi Jixu reaction after 1 hour, stopped reaction.Add elutriation and go out solid and filter, ethanol drip washing, toluene for crude product-ethanol system recrystallization, obtains solid intermediate G15-2, yield 70%.
(3) preparation of compound G15:
By 9.24g(0.01mole) intermediate G15-2, 3, 5-diphenyl benzene boric acid 2.74g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, stopped reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain white solid compound G15, yield 77%.MS(m/e): 1072.48, ultimate analysis: C 82h 60n 2, theoretical value C:91.76, H:5.63, N:2.61; Measured value C:91.80, H:5.65, N:2.55.
Embodiment 16: the preparation of compound G16
The preparation of the target compound G16 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000261
Concrete, the preparation of compound G16 comprises the following steps:
Intermediate G5-5 is provided, and described intermediate G5-5 is according to the method preparation in embodiment 5, by 8.25g(0.01mole) intermediate G5-5, triphenylene-2-boric acid 2.72g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml, pass into nitrogen 10 minutes, then add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, close heating, be spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing separates organic phase, be spin-dried for and used ethanol heat to boil twice, obtain faint yellow solid compound G16, yield 70%.MS(m/e): 972.39, ultimate analysis: C 73h 49fN 2, theoretical value C:90.09, H:5.08, F:1.95, N:2.88; Measured value C:90.05, H:4.95, F:2.02, N:2.98.
Embodiment 17: the preparation of compound G17
The preparation of the target compound G17 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000271
Concrete, the preparation of compound G17 comprises the following steps:
Intermediate B is provided, and described intermediate B is according to the method preparation in embodiment 15;
Intermediate G5-3 is provided, and described intermediate G5-3 is according to the method preparation in embodiment 5;
By 3.39g(0.01mole) intermediate G5-3,5.64g(0.01mole) intermediate B and the mixing of 50ml toluene, under nitrogen atmosphere, add 0.18g(0.0002mole) Pd 2(dba) 3, 1.44g(0.015mole) potassium tert.-butoxide and 0.809g(0.0004mole, 10 quality % toluene solutions) tri-butyl phosphine, be heated to reflux and react, some board monitoring, is cooled to room temperature after reacting completely, add 100ml toluene, cross silica gel funnel and obtain filtrate, filtrate water extraction obtains organic phase 3 times, is spin-dried for the rear silicagel column of crossing, obtain solid chemical compound G17, yield 75%.MS(m/e): 822.34, ultimate analysis: C 61h 43fN 2, theoretical value C:89.02, H:5.27, F:2.31N:3.40; Measured value C:89.02, H:5.30, F:2.34N:3.34.
Embodiment 18: the preparation of compound G18
The preparation of the target compound G18 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000272
Concrete, the preparation of compound G18 comprises the following steps:
(1) preparation of intermediate G18-1:
Intermediate B is provided, and described intermediate B is according to the method preparation in embodiment 15;
By 2.12g(0.01mole) diphenylene-oxide-4-boric acid, 5.65g(0.01mole) intermediate B, salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, finish reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain off-white color solid intermediate G18-1, yield 73%.
(2) preparation of intermediate G18-2:
By 6.52g(0.01mole) intermediate G18-1 adds in 100ml DMF, makes it to dissolve completely, drips 1.78g(0.01mole under stirring at room) the DMF solution (30 quality %) of NBS, 30 minutes used times, drip Bi Jixu reaction after 1 hour, stopped reaction.Add elutriation and go out solid and filter, ethanol drip washing, toluene for crude product-ethanol system recrystallization, obtains solid intermediate G18-2, yield 70%.
(3) preparation of compound G18:
By 7.31g(0.01mole) intermediate G18-2, fluoranthene-3-boric acid 2.46g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, finish reaction, reaction solution is spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain white solid compound G18, yield 73%.MS(m/e): 851.32, ultimate analysis: C 65h 41nO, theoretical value C:91.63, H:4.85, N:1.64, O:1.88; Measured value C:91.53, H:4.90, N:1.65, O:1.92.
Embodiment 19: the preparation of compound G19
First by following synthetic route, prepare intermediate C:
Figure BDA0000399101360000281
By 4.12g(0.01mle) intermediate A-7, a-iodine naphthalene 2.54g(0.01mole), salt of wormwood 4.14g(0.03mole), copper powder 0.064g(0.001mloe), phenanthroline 0.198g(0.001mole) and dimethylbenzene 50ml mix, be heated to reflux and react, point board monitoring is to after reacting completely, cooling, add toluene 100ml to filter, filtrate is spin-dried for, with ethanol-toluene system recrystallization, obtain solid intermediate C, yield 75%.MS(m/e): 563.12, ultimate analysis: C 37h 26brN, C:78.72, H:4.64, Br:14.15, N:2.48.
The compound G19 of the required preparation of the present embodiment, its structural formula and synthetic route are as follows:
Concrete, the preparation of compound G19 comprises the following steps
(1) preparation of intermediate G19-1:
Intermediate G1-2 is provided, and described intermediate G1-2 is according to the method preparation of embodiment 1;
By 5.38g(0.01mole) intermediate C, 4.11g(0.01mole) intermediate G1-2 and the mixing of 50ml toluene, under nitrogen atmosphere, add 0.18g(0.0002mole) Pd2 (dba) 3, 1.44g(0.015mole) potassium tert.-butoxide and 0.809g(0.0004mole, 10 quality % toluene solutions) tri-butyl phosphine, be heated to 70 ℃ and react, some board monitoring, is cooled to room temperature after reacting completely, add 100ml toluene, cross silica gel funnel and obtain filtrate, filtrate water extraction obtains organic phase 3 times, is spin-dried for the rear silicagel column of crossing, obtain solid intermediate G19-1, yield 75%.
(2) preparation of intermediate G19-2:
Add 8.69g(0.01mole) intermediate G19-1 adds in 100ml DMF, makes it to dissolve completely, drips 1.78g(0.01mole under stirring at room) the DMF solution (30 quality %) of NBS, 30 minutes used times, drip Bi Jixu reaction after 1 hour, stopped reaction.Add elutriation and go out solid and filter, ethanol drip washing, toluene for crude product-ethanol system recrystallization, obtains solid intermediate G19-2, yield 70%.
(3) preparation of compound G19:
By 9.48g(0.01mole) compound G19-2, fluoranthene-3-boric acid 2.46g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, finish reaction, be spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain white solid compound G19, yield 73%.MS(m/e): 1068.44, ultimate analysis: C 82h 56n 2, theoretical value C:92.10, H:5.28, N:2.62; Measured value C:92.10, H:5.30, N:2.60.
Embodiment 20: the preparation of compound G20
The preparation of the target compound G20 of the present embodiment, its structural formula and synthetic route are as follows:
Figure BDA0000399101360000301
Concrete, the preparation of compound G20 comprises the following steps:
(1) preparation of intermediate G20-1:
Intermediate C is provided, and described intermediate C is according to the method preparation of embodiment 19;
By 2.28g(0.01mole) dibenzothiophene-2-boric acid, 5.38g(0.01mole) intermediate C, salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, finish reaction, be spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain white solid intermediate G20-1, yield 70%.
(2) preparation of intermediate G20-2:
By 6.42g(0.01mole) intermediate G20-1 adds in 100ml DMF, makes it to dissolve completely, drips 1.78g(0.01mole under stirring at room) the DMF solution (30 quality %) of NBS, 30 minutes used times, drip Bi Jixu reaction after 1 hour, stopped reaction.Add elutriation and go out solid and filter, ethanol drip washing, toluene for crude product-ethanol system recrystallization, obtains solid intermediate G20-2, yield 72%.
(3) preparation of compound G20:
By 6.7g(0.01mole) compound G20-2, fluoranthene-3-boric acid 2.46g(0.01mole), salt of wormwood 4.15g(0.03mole), toluene 50ml, ethanol 30ml and water 30ml mix, under nitrogen atmosphere, add tetrakis triphenylphosphine palladium 0.23g(0.0002mole), being warming up to refluxes reacts, point board monitoring is to reacting completely, close heating, be spin-dried for, add 100ml methylene dichloride, make it dissolve complete and cross silicagel column, filtrate adds 100ml water, washing, separate organic phase, be spin-dried for and used ethanol heat to boil twice, filter, obtain white solid compound G20, yield 70%.MS(m/e): 841.28, ultimate analysis: C 63h 39nS, theoretical value C:89.86, H:4.67, N:1.66, S:3.81; Measured value C:89.81, H:4.70, N:1.63, S:3.86.
Application Example
Embodiment 21:
(1) device design
For the hole injection efficiency of comparative material, the EL device structure of the present invention's design is as follows: substrate/anode/hole injection layer (HIL)/hole transmission layer (HTL)/luminescent layer (EL)/electron transfer layer (ETL)/negative electrode.
Substrate can use traditional glass substrate or plastic base, and the present embodiment is selected glass substrate.
Anode can be used tin indium oxide (ITO), indium zinc oxide (IZO), tindioxide (SnO 2) etc., the present embodiment selects tin indium oxide (ITO) as anode.
Hole-injecting material as a comparison material can be used current TDATA, the 2-TNATA having reported, TCTA etc., the contrast material that the present embodiment selects 2-TNATA to inject as hole.
Hole mobile material can be used hole mobile material NPB, TPD etc. conventional in prior art, and the present embodiment selects NPB as hole mobile material.
Luminescent layer material of main part can be used CBP, ADN etc., and dopant material may use Ir (ppy) 3, TBPe etc., the present embodiment is selected CBP doping Ir (ppy) 3as luminescent layer material.
Electron transport material can be used BPhen, Alp 3, TPBi etc., the present embodiment is selected Alp 3as electron transport material.
Negative electrode can be used Mg (magnesium), Al (aluminium), Ag(silver) etc., the present embodiment selects Al as cathode material.
Above-mentioned mentioned material structure is as follows:
Figure BDA0000399101360000321
Figure BDA0000399101360000331
(2) fabricate devices
The preparation of comparative device 1:
By the glass substrate that has been coated with ITO with clean-out system ultrasonic lower cleaning 5 minutes, then use successively ionized water ultrasonic 5 minutes, ultrasonic 5 minutes of isopropanol solvent, is baked to moisture content and removes completely after taking-up, then uses UV-light and ozone clean 20 minutes.
The above-mentioned glass substrate with anode is placed in to vacuum evaporation equipment, and on anode tunic, vacuum evaporation 2-TNATA is as hole injection layer, and evaporation thickness is 80nm;
On above-mentioned hole injection layer film, vacuum evaporation NPB is as hole transmission layer, and evaporation thickness is 20nm;
Vacuum evaporation luminescent layer on above-mentioned hole transmission layer, evaporation CBP and Ir (ppy) 3, evaporation total film thickness is 30nm;
Vacuum evaporation Alp on above-mentioned luminescent layer 3as electron transfer layer, evaporation total thickness is 80nm;
On electron transfer layer, vacuum evaporation Al layer is as the negative electrode of device, and thickness is 150nm.
Use compound of the present invention as the preparation of the device of hole-injecting material:
Preparation method is identical with aforesaid method, only changes the compound of hole injection layer, specifically refers to table 1.
The device performance preparing is in Table 1(device architecture: ITO/ hole injection layer (80nm)/NPB(20nm)/CBP:5%Ir (ppy) 3(30nm)/Alp 3(80nm)/Al(150nm).
Table 1
Figure BDA0000399101360000332
Embodiment 21 results show, while using compound of the present invention as the material of hole injection layer, it has electrical characteristic and the charge transport ability of improving device, device 1 to device 10 adopts respectively compound of the present invention as the hole injection layer material of organic electroluminescence device, compare with comparative device 1, reduced significantly the trigger voltage of device, improved device current efficiency, made device there is the longer half-life simultaneously.
Embodiment 22:
The preferred implementation of fabricate devices:
According to the method fabricate devices of embodiment 21, difference is to change the material of the hole transmission layer in device.Specifically refer to table 2.
The device preparation method of test material is identical with example 2, only changes the compound of hole transmission layer.The performance of concrete device refers to table 2.
Table 2
Figure BDA0000399101360000342
Figure BDA0000399101360000351
Embodiment 22 results show, while using compound of the present invention as the material of hole transmission layer, it has electrical characteristic and the charge transport ability of improving device, device 11 to device 20 adopts respectively type material of the present invention as the hole transport layer material of organic electroluminescence device, compare with comparative example 2, reduced significantly the trigger voltage of device, improved device current efficiency, made device there is the longer half-life simultaneously.
Embodiment 23:
(1) design of comparative device 3
Performance for comparative material optically coupled layers (CPL), the EL device structure of the present invention's design as shown in Figure 1, comprising: substrate/reflection anode/hole injection layer (HIL)/hole transmission layer (HTL)/luminescent layer (EL)/electron transfer layer (ETL)/transparent cathode/optically coupled layers (CPL).
Substrate can use traditional glass substrate or plastic base, and the present embodiment is selected glass substrate.
Reflection anode can be used Mg (magnesium), Al (aluminium), Ag(silver) etc., the present embodiment selects Ag as transparent cathode material.
Hole-injecting material can be used current TDATA, the 2-TNATA having reported, TCTA etc., and the present embodiment selects 2-TNATA as hole-injecting material.
Hole mobile material can be used hole mobile material NPB, TPD etc. conventional in prior art, and the present embodiment selects NPB as hole mobile material.
Luminescent layer material of main part can be used CBP, ADN etc., and dopant material may use Ir (ppy) 3, TBPe etc., the present embodiment selects ADN doping TBPe as luminescent layer material.
Electron transport material can be used BPhen, Alp 3, TPBi etc., the present embodiment selects BPhen as electron transport material.
Transparent cathode can be used Mg (magnesium), Al (aluminium), Ag(silver), MgAg etc., the present embodiment selects MgAg as transparent cathode material.
Optical coupled layer material can be used Alp 3, NPB etc., the present embodiment selects NPB as optical coupled layer material.
The structure of above-mentioned materials is as shown in embodiment 21.
(2) prepare comparative device 3
By the glass substrate that has been coated with reflection anode with clean-out system ultrasonic lower cleaning 5 minutes, then use successively ionized water ultrasonic 5 minutes, ultrasonic 5 minutes of isopropanol solvent, is baked to moisture content and removes completely after taking-up, then uses UV-light and ozone clean 20 minutes.
The above-mentioned glass substrate with reflection anode is placed in to vacuum evaporation equipment, and on anode tunic, vacuum evaporation 2-TNATA is as hole injection layer, and evaporation thickness is 80nm;
On above-mentioned hole injection layer film, vacuum evaporation NPB is as hole transmission layer, and evaporation thickness is 20nm;
Vacuum evaporation luminescent layer on above-mentioned hole transmission layer, evaporation AND and TBPe, evaporation total film thickness is 30nm;
On above-mentioned luminescent layer, vacuum evaporation BPhen is as electron transfer layer, and evaporation total thickness is 80nm;
On electron transfer layer, vacuum evaporation MgAg layer is as the transparent cathode of device, and thickness is 5nm.
Vacuum evaporation optically coupled layers NPB on transparent cathode layer, thickness is 150nm.
Use compound of the present invention as the preparation of the device of hole-injecting material:
Device 31-40 preparation method is identical with the preparation method of comparative device 3, only changes the compound of optical coupled layer material.Specifically refer to table 3
Device performance is in Table 3(device architecture: reflection anode/2-TNATA(80nm)/NPB(20nm)/AND:5%TBPe (30nm)/BPhen(80nm)/MgAg(5nm)/optically coupled layers (150nm).
Table 3
Figure BDA0000399101360000361
Embodiment 23 results show, use compound of the present invention as optical coupled layer material, not only there is electrical characteristic and the charge transport ability of improving device, and can significantly improve the purity of light, device 31 to device 40 adopts respectively type material of the present invention as the optical coupled layer material of organic electroluminescence device, with comparative device 3 relatively, not only reduced the trigger voltage of device, improve device current efficiency, made device there is the longer half-life, improved the purity of light simultaneously.
Although above embodiment describes the present invention, the present invention is not limited to above-described embodiment, should be appreciated that those skilled in the art can make various modifications and improvement under the scope of the present invention's design.

Claims (10)

1. an organic compound, it has suc as formula the structure shown in I:
Wherein:
R 1, R 2and R 3be selected from independently of one another hydrogen atom, replacement or unsubstituted C1-C30 alkyl, replacement or unsubstituted C1-C30 cycloalkyl, replacement or unsubstituted C1-C30 alkoxyl group, replacement or unsubstituted C6-C30 aryl, replacement or do not replace C6-C30 aryloxy, replacement or do not replace C6-C30 aryl amine, replacement or unsubstituted C2-C30 heterocycle, replacement or do not replace C6-C30 thick and many cyclic groups, hydroxyl, cyano group or replace unsubstituted amino.
2. compound according to claim 1, is characterized in that, described C6-C30 aryl is selected from phenyl, xenyl, naphthyl or anthryl.
3. compound according to claim 1, is characterized in that, described compound is selected from the compound with the structure shown in G1-G20:
Figure FDA0000399101350000012
Figure FDA0000399101350000021
Figure FDA0000399101350000031
Figure FDA0000399101350000041
4. an electroluminescent device, comprises in right to use requirement 1-3 that at least one in the compound described in any one is as hole injection layer and/or hole transmission layer.
5. electroluminescent device according to claim 4, is characterized in that, described device comprises substrate and is cascadingly set on anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the negative electrode on substrate.
6. electroluminescent device according to claim 5, is characterized in that, described device also comprises optically coupled layers, on its setting and described negative electrode.
7. according to the electroluminescent device described in any one in claim 6, it is characterized in that, the material of described optically coupled layers is selected from claim 1-3 at least one in the compound described in any one.
8. according to the electroluminescent device described in any one in claim 4-7, it is characterized in that, described anode material is selected from least one in tin indium oxide, indium zinc oxide and tindioxide.
9. according to the electroluminescent device described in any one in claim 4-8, it is characterized in that, described luminescent layer material is selected from two carbazole biphenyl, 9,10-bis-(2-naphthyl) anthracene, Ir (ppy 3) or two carbazole biphenyl and the Ir (ppy of TPBi doping 3) or TPBi doping 9, at least one in 10-bis-(2-naphthyl) anthracene.
10. according to the electroluminescent device described in any one in claim 4-9, it is characterized in that, described electric transmission layer material is selected from 4,7-phenylbenzene-1, at least one in 10-phenanthroline and three (oxine) aluminium.
CN201310495246.6A 2013-10-21 2013-10-21 A kind of organic compound and use the electroluminescent device of this organic compound Active CN103524399B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310495246.6A CN103524399B (en) 2013-10-21 2013-10-21 A kind of organic compound and use the electroluminescent device of this organic compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310495246.6A CN103524399B (en) 2013-10-21 2013-10-21 A kind of organic compound and use the electroluminescent device of this organic compound

Publications (2)

Publication Number Publication Date
CN103524399A true CN103524399A (en) 2014-01-22
CN103524399B CN103524399B (en) 2016-03-02

Family

ID=49926805

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310495246.6A Active CN103524399B (en) 2013-10-21 2013-10-21 A kind of organic compound and use the electroluminescent device of this organic compound

Country Status (1)

Country Link
CN (1) CN103524399B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014178434A1 (en) * 2013-05-02 2014-11-06 出光興産株式会社 Compound, material for organic electroluminescent elements, organic electroluminescent element, and electronic device
WO2017138755A1 (en) * 2016-02-11 2017-08-17 주식회사 엘지화학 Heterocyclic compound and organic electroluminescent device containing same
CN107266456A (en) * 2017-07-13 2017-10-20 长春海谱润斯科技有限公司 A kind of electroluminescent organic material and its organic luminescent device with hole transport effect
WO2018083053A1 (en) * 2016-11-02 2018-05-11 Merck Patent Gmbh Materials for electronic devices
JP2018172319A (en) * 2017-03-31 2018-11-08 出光興産株式会社 Novel compound, organic electroluminescent element, and electronic apparatus
CN111051293A (en) * 2017-09-08 2020-04-21 默克专利有限公司 Material for electronic devices
US10680183B2 (en) 2015-02-15 2020-06-09 Universal Display Corporation Organic electroluminescent materials and devices

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101248156A (en) * 2005-08-26 2008-08-20 默克专利有限公司 Novel materials for organic electroluminescent devices
CN101321728A (en) * 2005-12-02 2008-12-10 东洋油墨制造株式会社 Diaminoarylene compound having carbazolyl group and use thereof
CN102473859A (en) * 2010-07-26 2012-05-23 出光兴产株式会社 Organic electroluminescent element
CN103030585A (en) * 2011-10-10 2013-04-10 三星显示有限公司 Heterocyclic compound, organic light-emitting diode and flat panel display device
CN103086953A (en) * 2011-11-03 2013-05-08 三星显示有限公司 Heterocyclic compound and organic light-emitting device including the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101248156A (en) * 2005-08-26 2008-08-20 默克专利有限公司 Novel materials for organic electroluminescent devices
CN101321728A (en) * 2005-12-02 2008-12-10 东洋油墨制造株式会社 Diaminoarylene compound having carbazolyl group and use thereof
CN102473859A (en) * 2010-07-26 2012-05-23 出光兴产株式会社 Organic electroluminescent element
CN103030585A (en) * 2011-10-10 2013-04-10 三星显示有限公司 Heterocyclic compound, organic light-emitting diode and flat panel display device
CN103086953A (en) * 2011-11-03 2013-05-08 三星显示有限公司 Heterocyclic compound and organic light-emitting device including the same

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2014178434A1 (en) * 2013-05-02 2017-02-23 出光興産株式会社 COMPOUND, MATERIAL FOR ORGANIC ELECTROLUMINESCENT ELEMENT, ORGANIC ELECTROLUMINESCENT ELEMENT AND ELECTRONIC DEVICE
WO2014178434A1 (en) * 2013-05-02 2014-11-06 出光興産株式会社 Compound, material for organic electroluminescent elements, organic electroluminescent element, and electronic device
US10680183B2 (en) 2015-02-15 2020-06-09 Universal Display Corporation Organic electroluminescent materials and devices
CN108602836B (en) * 2016-02-11 2020-12-25 株式会社Lg化学 Heterocyclic compound and organic electroluminescent element comprising same
WO2017138755A1 (en) * 2016-02-11 2017-08-17 주식회사 엘지화학 Heterocyclic compound and organic electroluminescent device containing same
KR20170094767A (en) * 2016-02-11 2017-08-21 주식회사 엘지화학 Heterocyclic compound and organic light emitting device comprising the same
KR101879121B1 (en) * 2016-02-11 2018-07-18 주식회사 엘지화학 Heterocyclic compound and organic light emitting device comprising the same
CN108602836A (en) * 2016-02-11 2018-09-28 株式会社Lg化学 Heterocyclic compound and organic electroluminescent device comprising it
WO2018083053A1 (en) * 2016-11-02 2018-05-11 Merck Patent Gmbh Materials for electronic devices
CN109890787A (en) * 2016-11-02 2019-06-14 默克专利有限公司 Material for electronic device
US11302870B2 (en) * 2016-11-02 2022-04-12 Merck Patent Gmbh Materials for electronic devices
JP2018172319A (en) * 2017-03-31 2018-11-08 出光興産株式会社 Novel compound, organic electroluminescent element, and electronic apparatus
CN107266456A (en) * 2017-07-13 2017-10-20 长春海谱润斯科技有限公司 A kind of electroluminescent organic material and its organic luminescent device with hole transport effect
JP2020533325A (en) * 2017-09-08 2020-11-19 メルク パテント ゲーエムベーハー Materials for electronic devices
CN111051293A (en) * 2017-09-08 2020-04-21 默克专利有限公司 Material for electronic devices
JP7286625B2 (en) 2017-09-08 2023-06-05 メルク パテント ゲーエムベーハー Materials for electronic devices
CN111051293B (en) * 2017-09-08 2024-02-13 默克专利有限公司 Material for electronic devices

Also Published As

Publication number Publication date
CN103524399B (en) 2016-03-02

Similar Documents

Publication Publication Date Title
CN103524399B (en) A kind of organic compound and use the electroluminescent device of this organic compound
KR100901888B1 (en) Novel organometalic compounds for electroluminescence and organic electroluminescent device using the same
KR101344787B1 (en) Compound for organic optoelectronic device, organic light emitting diode including the same and display including the organic light emitting diode
JP5406305B2 (en) Electroluminescent device using electroluminescent compound as luminescent material
TWI461507B (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN104987309B (en) A kind of symmetrical derivative host material of phenanthro- imidazoles and electroluminescent device
CN104342126B (en) Organic electroluminescent material and organic electroluminescent device
KR20110132721A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN105753629B (en) Compound and the Organnic electroluminescent device for using it
KR20100047466A (en) Novel compounds for electronic material and organic electronic device using the same
CN104045595A (en) Organic compound and electroluminescent device using same
KR101667369B1 (en) Multicyclic aromatic compound and organic light emitting device using the same
KR20100048203A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN105294663B (en) One kind containing pyridine compounds and its organic electroluminescence device
KR20120029751A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN102459507A (en) Compound for an organic photoelectric element, and an organic photoelectric element comprising the same
WO2011014039A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
TW201329059A (en) Aromatic amine derivative, material for organic electroluminescent element, and organic electroluminescent element
KR20110098293A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
KR20120038056A (en) Novel compounds for organic electronic material and organic electroluminescent device using the same
KR20120044523A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN109336772A (en) A kind of triaromatic amine compound containing spiro structure and application thereof and luminescent device
JP2009137941A (en) New organic electroluminescent compound and organic electroluminescent device by using the same
JP2023500009A (en) Heterocyclic compound, organic light-emitting device containing the same, composition for organic layer of organic light-emitting device, and method for manufacturing organic light-emitting device
CN102031104A (en) Bipolar phosphorescent main material containing anthracene derivatives of tetraphenyl silicane and carbazole and organic electroluminescent device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information

Address after: 102299, Beijing, Changping District, super road 37, No. 5, building 2

Applicant after: The green people's science and technology limited Company in Beijing

Address before: 100085 B223 room, No. 5, Pioneer Road, Beijing, Haidian District

Applicant before: The green people's science and technology limited Company in Beijing

COR Change of bibliographic data
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20180612

Address after: 057750 Handan, Guantao, Hebei province Shoushan Temple Township, Ma Ha Zhai village west (new chemical industry park management committee room 208)

Patentee after: Hebei Huaqing photoelectric material Co., Ltd.

Address before: 102299 2 floor, No. 37, No. 5, Changping District Chao Qian Road, Beijing

Patentee before: The green people's science and technology limited Company in Beijing